Arrow pushing
Arrow pushing or electron pushing is a technique used to describe the progression of
Arrow pushing has been extended to inorganic chemistry, especially to the chemistry of s- and p-block elements. It has been shown to work well for hypervalent compounds.[2]
Notation
The representation of reaction mechanisms using curved arrows to indicate electron flow was developed by
When a bond is broken, electrons leave where the bond was; this is represented by a curved arrow pointing away from the bond and ending with the arrow pointing towards the next unoccupied molecular orbital. The electrons can be transferred to a specific atom or can be transferred to a single (sigma) bond, thus making it a double (pi) bond, but the arrow is always pointing towards a specific atom, because electrons always move to a new atom whenever they are "pushed". Organic chemists represent the formation of a bond by a curved arrow pointing between two species.[7]
For clarity, when pushing arrows, it is best to draw the arrows starting from a lone pair of electrons or a σ or π bond and ending in a position that can accept a pair of electrons, allowing the reader to know exactly which electrons are moving and where they are ending. Bonds are broken in places where a corresponding antibonding orbital is filled. Some authorities[1] allow the simplification that an arrow can originate at a formal negative charge that corresponds to a lone pair. However, not all formal negative charges correspond to the presence of a lone pair (e.g., the B in F4B−), and care needs to be taken with this usage.
Breaking of bonds
A
Homolytic bond cleavage
Homolytic
For example,
Heterolytic bond cleavage
Heterolytic bond cleavage is a process where the electron pair that comprised a bond moves to one of the atoms that was formerly joined by a bond. The bond breaks, forming a negatively charged
Acid-base reactions
A Lewis acid-base reaction occurs when a molecule with a lone electron pair, or a base, donates its electrons to an electron-pair acceptor, also known as an acid.[11] This can be shown in a reaction with a curved arrow pointing from the nonbonding electron pair to the electron acceptor. In a reaction involving Brønsted-Lowry acids and bases, the arrows are used in the same manner, and they help to indicate the attacking proton.[12] In a Brønsted-Lowry acid-base reaction the arrow will begin from the acid, the proton acceptor, to the base, the proton donor.[13]
SN1 reactions
An SN1 reaction occurs when a molecule separates into a positively charged component and a negatively charged component. This generally occurs in highly polar solvents through a process called solvolysis. The positively charged component then reacts with a nucleophile forming a new compound. SN1 reactions are reactions whose rate is dependent only on haloalkane concentration.
In the first stage of this reaction (solvolysis), the C-L bond breaks and both electrons from that bond join LG (the leaving group) to form LG− and R3C+ ions. This is represented by the curved arrow pointing away from the C-LG bond and towards LG. The nucleophile Nu−, being attracted to the R3C+, then donates a pair of electrons forming a new C-Nu bond.
Because an SN1 reaction proceeds with the Substitution of a leaving group with a Nucleophile, the SN designation is used. Because the initial solvolysis step in this reaction involves a single molecule dissociating from its leaving group, the initial stage of this process is considered a uni-molecular reaction. The involvement of only 1 species in the initial phase of the reaction enhances the mechanistic designation to SN1.[14] An SN1 reaction has two steps.
SN2 reactions
An SN2 reaction occurs when a nucleophile displaces a leaving group residing on a molecule from the backside of the leaving group. This displacement or substitution results in the formation of a substitution product with inversion of stereochemical configuration. The nucleophile forms a bond with its lone pair as the electron source. The electron sink which ultimately accepts the electron density is the nucleofuge (leaving group), with bond forming and bond breaking occurring simultaneously at the transition state (marked with a double-dagger). The rates of SN2 reactions are dependent on the concentration of the haloalkane and the nucleophile.
Because an SN2 reaction proceeds with the substitution of a leaving group with a nucleophile, the SN designation is used. Because this mechanism proceeds with the interaction of two species at the transition state, it is referred to as a bimolecular process, resulting in the SN2 designation.[15] An SN2 reaction is a concerted process, which means that the bonds are breaking and forming concurrently. Thus, the electron movement shown by the arrow pushing is happening simultaneously.[16] An SN2 reaction has one step.
E1 eliminations
An E1 elimination occurs when a proton adjacent to a positive charge leaves and generates a double bond.
Because initial formation of a
E1 eliminations proceed with the Elimination of a leaving group leading to the E designation. Because this mechanism proceeds with the initial dissociation of a single starting material forming a carbocation, this process is considered a uni-molecular reaction. The involvement of only 1 species in the initial phase of the reaction enhances the mechanistic designation to E1.
E2 eliminations
An E2 elimination occurs when a proton adjacent to a leaving group is extracted by a base with simultaneous elimination of a leaving group and generation of a double bond.
Similar to the relationship between E1 eliminations and SN1 mechanisms, E2 eliminations often occur in competition with SN2 reactions. This observation is most often noted when the base is also a nucleophile. In order to minimize this competition, non-nucleophilic bases are commonly used to effect E2 eliminations.
E2 eliminations proceed through initial extraction of a proton by a base or nucleophile leading to Elimination of a leaving group justifying the E designation. Because this mechanism proceeds through the interaction of two species (substrate and base/nucleophile), E2 reactions are recognized as bi-molecular. Thus, the involvement of 2 species in the initial phase of the reaction enhances the mechanistic designation to E2.
Addition reactions
, the result is a 1,2-addition. When a nucleophile adds to a conjugated carbonyl system, the result is a 1,4-addition. The designations 1,2 and 1,4 are derived from numbering the atoms of the starting compound where the oxygen is labeled “1” and each atom adjacent to the oxygen are sequentially numbered out to the site of nucleophilic addition. A 1,2-addition occurs with nucleophilic addition to position 2 while a 1,4-addition occurs with nucleophilic addition to position 4.Addition-elimination reactions
Addition-elimination reactions are addition reactions immediately followed by elimination reactions. In general, these reactions take place when esters (or related functional groups) react with nucleophiles. In fact, the only requirement for an addition-elimination reaction to proceed is that the group being eliminated is a better leaving group than the incoming nucleophile.
See also
Notes
- ^ ISBN 978-0-19-850346-0.
- ^ Abhik Ghosh, Steffen Berg, Arrow Pushing in Inorganic Chemistry: A Logical Approach to the Chemistry of the Main Group Elements, (John Wiley & Sons, 2014).
- .
- S2CID 252883623.
- ^ Ball, Philip (2022-02-14). "A century of curly arrows". chemistryworld.com. Retrieved 2022-12-22.
- )
- ^ "Notes on arrow pushing (curly arrows)" (PDF). Imperial College London. Retrieved 2009-04-27.
- ^ "Free Radical Reactions -- One Electron Intermediates". Washington State University. Retrieved 2009-05-02.
- ^ "3.3: Arrow Conventions". Chemistry LibreTexts. 2019-04-15. Retrieved 2022-11-18.
- ^ Liu, Xin (2021-12-09). "9.1 Homolytic and Heterolytic Cleavage". Organic Chemistry I. Pressbooks.
- ^ "The Lewis Definitions of Acids and Bases". chemed.chem.purdue.edu. Retrieved 2022-11-18.
- ^ Richardson, Jacquie (2020-09-16). "Loudon Ch. 3 Review: Acids/Bases/Curved Arrows" (PDF).
- ^ "Brønsted Acids and Bases". chemed.chem.purdue.edu. Retrieved 2022-11-18.
- ^ "11.5: Characteristics of the SN1 Reaction". Chemistry LibreTexts. 2015-05-03. Retrieved 2022-10-31.
- ^ "11.3: Characteristics of the SN2 Reaction". Chemistry LibreTexts. 2015-05-03. Retrieved 2022-10-31.
- OCLC 729915305.
References
- Daniel E. Levy, Arrow-Pushing in Organic Chemistry: An Easy Approach to Understanding Reaction Mechanisms - Second Edition, (John Wiley & Sons, 2017)
- Daniel P. Weeks, Pushing Electrons: A Guide for Students of Organic Chemistry, (Brooks Cole, 1998)
- Abhik Ghosh, Steffen Berg, Arrow Pushing in Inorganic Chemistry: A Logical Approach to the Chemistry of the Main Group Elements, (John Wiley & Sons, 2014)
- Robert B. Grossman, The Art of Writing Reasonable Organic Reaction Mechanisms, (Springer, 2007)
External links
- MIT.edu, OpenCourseWare: Organic Chemistry I
- HaverFord.edu, Organic Chemistry Lectures, Videos and Text
- CEM.MSU.edu, Virtual Textbook of Organic Chemistry